29Si固体核磁共振技术在C-S-H凝胶中的应用进展

C-S-H凝胶作为硅酸盐水泥最主要的水化产物,是影响水泥混凝土行业工程质量的重要因素.本文围绕29Si固体核磁共振技术(29Si NMR)在硅酸盐水泥水化产物应用展开,从水化硅酸钙晶型、C-S-H聚合机理、钙硅比、机械力活化作用、矿物掺合料对C-S-H影响等几方面阐述29Si NMR在硅酸盐水泥水化产物C-S-H凝胶中的应用,提出了利用29Si NMR分析硅酸盐水泥水化产物存在的问题,并展望了29Si NMR在水泥水化领域的发展趋势.     

C-S-H凝胶分子结构研究进展

水化硅酸钙(C-S-H)凝胶是硅酸盐水泥的主要水化产物,是水泥胶凝能力的主要来源。C-S-H凝胶的纳米结构由长程无序、短程有序的类Tobermorite纳米晶组成。明确类Tobermorite相纳米晶的分子结构、氢键等分子间作用力组成及性质、H2O和羟基基团与硅氧主链的相互作用机理对理解C-S-H凝胶的胶凝能力形成机理、调控水化产物的胶凝能力具有重要意义。本文在总结固体核磁共振分析技术研究C-S-H凝胶硅氧主链结构研究进展的基础上,提出其钙硅比对硅氧主链聚合度和平均链长的影响规律,并运用固体核磁测试与第一性原理计算核磁结果相结合的研究方法,揭示了C-S-H凝胶分子结构中氢键的组成及性质,明确了水分子及羟基基团与硅氧主链的相互作用机理。     

不同钙硅比C-S-H对多种重金属离子的俘获及其稳定性

通过溶液法人工合成不同C/S的C-S-H,分析比较了C-S-H对多种重金属离子俘获能力及其稳定性.研究结果表明,多种重金属离子共存下,低钙硅比C-S-H对重金属离子俘获主要以物理吸附为主,高钙硅比C-S-H对重金属离子的俘获则以化学结合主,其对重金属离子固化作用较前者稳定.无论钙硅比高低,多种离子共存下,C-S-H对Cu2+、Cd2+离子均有很强的固化能力,但对Pb2+离子的固化及稳定性较差.重金属离子价态不同,C-S-H俘获固化作用存大巨大差异,C-S-H对Cr3+俘获作用较强,但对Cr6+固化不起主要作用且稳定性较差.水化液相中Cr6+离子的存在,对pb2+离子在C-S-H中固化有极大影响.     

C-S-H凝胶对Pb(Ⅱ)的吸附固化作用

以分析纯Ca(NO3)2·4H2O、Na2SiO3·9H2O、Pb(NO3)2为原料,通过溶液反应法,制备纯净的C-S-H凝胶和掺杂Pb的C-S-H凝胶,研究了C-S-H凝胶在形成过程中对Pb的吸附固化作用及掺杂Pb后C-S-H凝胶的结构变化.结果表明,可溶铅盐由2％增至6％时,C-S-H凝胶对Pb均有良好的吸附固化作用,俘获Pb总量增大.XRD图谱发现掺杂Pb的C-S-H凝胶,其主峰位置发生偏移,出现明显的Ca(OH)2衍射峰.红外测试表明含Pb C-S-H凝胶硅氧四面体的链接方式发生变化,Q2伸缩振动峰向低波数方向偏移,Q1伸缩振动峰吸收强度增加.     

纳米无定形C-S-H凝胶颗粒及其结构表征

以无水氯化钙( CaCl2)和水玻璃为原料,通过室温沉淀反应制备了水化硅酸钙(C-S-H)凝胶颗粒.采用SEM、FTIR、XRD、XRF、TEM等对不同C/S和pH值条件下制备的C-S-H凝胶颗粒的形貌和结构进行了表征.结果表明,较低pH值条件下制备的C-S-H凝胶颗粒间呈现不同程度的团聚,-Si-O键之间显示一定的聚合度,其平均粒径在15 ～25nm之间,且呈无定形结构;在pH值较高时,该凝胶颗粒呈半结晶结构.     

固体核磁共振技术在C-S-H中的研究进展

C-S-H是水泥水化的主要胶凝材料,其结构直接影响混凝土工程性,由于其结晶度较低,中短程有序,采用固体核磁(NMR)可作为分析其结构的方法之一。本文从C-S-H的模型,NMR中特征参数,平均分子链长(MCL)和聚合度三个角度,对水化龄期、掺合料、钙硅比三个方面进行了综述,并展望了固体核磁技术在C-S-H中的发展趋势。     

C-S-H 凝胶及其研究方法

在分析C-S-H凝胶的复杂性和特征的基础上,就测定它的化学组成、C-S-H凝胶中[SiO4]4-四面体的聚合度及其结构的化学和物理的方法作了简要介绍.现代各种测试方法的出现和使用,对C-S-H凝胶的组成和集中[SiO4]4-四面体的聚合结构有了较为完整的概念.     

C-S-H/PCE凝胶对掺磷渣水泥的低温促凝早强性能研究

探讨C-S-H/PCE凝胶对掺磷渣硅酸盐水泥的低温促凝早强性能的影响,并通过上清液pH值、Ca²⁺浓度和化学结合水量分析其对水化的影响机理。低温下(8℃) C-S-H/PCE凝胶能有效缩短混凝土终凝时间,并提高早期强度,当掺量5%时,混凝土终凝时间缩短近6 h,16 h、24 h和3 d抗压强度比分别为160%、150%和110%,且不影响2.5 h混凝土工作性能。C-S-H/PCE凝胶能使低温下掺磷渣硅酸盐水泥浆体处于高pH状态,加速早期水泥矿相离子溶解,提高Ca²⁺过饱和度,加速后期析晶过程,提高化学结合水量,从而促进掺磷渣硅酸盐水泥的水化,实现低温促凝早强。     

纳米C-S-H对矿粉-水泥体系水化的影响

C-S-H是通用硅酸盐水泥主要的水化产物,对水泥基材料的性能起着十分重要的作用,但水泥水化产物复杂,难以从水化产物中分离出纯净的C-S-H并研究其对水泥基材料的影响。故本文通过双分解法制备了纳米C-S-H(NC)颗粒,并将其掺入矿粉-水泥体系中,通过无接触式电阻率测定仪、X射线衍射仪、差热分析仪(DSC-TG)、扫描电镜、压汞测试仪(MIP)等探究了NC对矿粉-水泥体系水化的影响。研究发现,在1%~4%(质量分数)掺量范围内,掺入NC可缩短基体的凝结时间,并为水泥早期水化提供更多的活性位点,加速水化产物的形成和沉淀,促进水化产物之间的搭接,从而降低了基体孔隙率并使基体早期强度和水化浆体电阻率均有所提升。     

基于不同理论的C-S-H凝胶模型及结构参数表征研究进展

硅酸钙凝胶(C-S-H凝胶)是硅酸盐水泥主要水化产物,也是硬化水泥石强度重要来源。本文系统阐释了基于不同理论所得出的C-S-H凝胶结构模型,包括泰勒模型(Taylor模型)、固溶模型、瑞迟德森-格夫斯模型(R-G模型)、纳米结构模型(CM模型)、固相-液相-凝胶体系模型(SLGS模型)、三维介观结构模型,重点介绍了SLGS模型和三维介观结构模模型。并结合现有的研究进展对C-S-H凝胶的钙硅摩尔比、含水量、聚合度、硬度等的结构参数及其表征方法进行了介绍。     

Composition and structure of C-S-H in white Portland cement-20% metakaolin pastes hydrated at 25 °C

The microstructure and composition of water- and alkali-activated hardened pastes of white Portland cement-20% metakaolin blends have been studied using solid-state NMR spectroscopy and analytical TEM. The results show that after hydration for 1 day nearly half the cement had reacted in the water-activated paste but very little, if any, of the metakaolin; by 28 days two-thirds of the cement had reacted and most of the metakaolin. In contrast, whilst alkali-activation again led to about half the cement reacting by 1 day, about a quarter of the metakaolin had also reacted; and whilst most of the metakaolin had again reacted by 28 days, there had been no further reaction of the cement. The high degree of reaction of the MK in both pastes at 28 days resulted in long-chain highly aluminous C-S-H, with most of the bridging sites occupied by Al³⁺ rather than Si⁴⁺. The data for the C-S-H in the water-activated paste are consistent with both the tobermorite/jennite (T/J) and tobermorite/calcium hydroxide (T/CH) models for the nanostructure of C-S-H - although very little J- or CH-like structure is needed to account for the observed compositions - whilst those for the alkali-activated paste can only be accounted for on the T/CH viewpoint.     

A colloidal interpretation of chemical aging of the C-S-H gel and its effects on the properties of cement paste

The properties, structure, and behavior of cement paste, including surface area, drying shrinkage, creep, and permeability are discussed with the assumption that the C-S-H gel is an aggregation of precipitated, colloidal-sized particles that undergoes chemical aging. A basic thesis of this paper is that C-S-H particles bond together over time, increasing the average degree of polymerization of the silicate chains and causing the C-S-H to become stiffer, stronger, and denser. This process occurs slowly at ambient temperatures, but can be greatly accelerated by elevated temperature curing and is also encouraged by drying, which introduces large local strains that may provide a microstructural basis for creep sites. This chemical aging process of C-S-H can thus affect many of the physical properties of cement paste, and there is particular relevance for the complex shrinkage and creep behavior of this material. The effects of a short heat treatment, which causes rapid aging, depend strongly on the moisture of the paste when it is heated. Many of the observations and insights presented here are not new. The primary objective of this paper is to demonstrate, by reporting a variety of published findings in one place, the significant amount of evidence that has been generated over the past 50 years favoring this interpretation. Another objective is to show that the properties and behavior of the C-S-H gel, and of cement paste, do not require a layered microstructure. Separating chemical aging effects from other changes, such as continued hydration, may well lead to a better understanding of the microstructural causes of creep and shrinkage.     

New insights into the effects of sugar on the hydration and microstructure of cement pastes

The effects of adding sugar to cement paste on hydration and microstructure were observed. While 1% sugar delayed hydration as expected, the delay period was shortened by increased curing temperature. When samples containing sugar began to react, hydration progressed very quickly and the degree of hydration soon surpassed that of control samples. Sugar addition increased the surface area and altered the pore size distribution, as measured by nitrogen, of cement pastes. Results indicate that sugar not only alters the rate of cement paste hydration, but the microstructure of calcium-silicate-hydrate (C-S-H) as well.     

C-S-H纳米晶核对矿物掺合料复合胶凝材料水化性能的影响研究

水泥中掺入大量矿物掺合料易造成其早期强度低、施工周期长等问题。本文研究了C-S-H晶核对含矿物掺合料的复合胶凝材料体系水化性能的影响规律;通过热力学计算阐述了C-S-H晶核降低水化产物成核势垒的机理,并通过离子溶出与沉积探讨大掺量矿物掺合料胶凝体系水化机理。结果表明：矿物掺合料复合胶凝材料体系水化能力较弱,这是由于Ca²⁺溶出受到制约,C₃S的水化反应缓慢;当加入晶核后,水泥中硅酸盐相溶解-结晶能力得到大幅提升,使得矿物掺合料水泥体系的水化反应活性接近纯水泥体系。研究表明,C-S-H晶核可解决大掺量矿物掺合料胶凝体系所带来的水化能力严重不足问题。     

Composition, morphology and nanostructure of C-S-H in white Portland cement pastes hydrated at 55 °C

The C-S-H present in water- and alkali-activated hardened pastes of white Portland cement hydrated at 55 °C has been characterized. The mean length of the aluminosilicate anions in the C-S-H was similar in both systems and increased with age. Inner product C-S-H generally had a fine scale, homogeneous morphology. Outer product C-S-H was generally fibrillar with water, and foil- or lath-like with alkali. There were some regions of C-S-H with coarse morphology. It was not possible to determine the chemical composition of C-S-H using the SEM; TEM-EDX was necessary. The C-S-H formed in the alkali-activated paste had a lower mean Ca/(Al + Si) ratio than that formed with water, which was offset by a larger quantity of calcium hydroxide. The potassium in the KOH-activated paste was present either within the C-S-H structure charge balancing the substitution of Al³⁺ for Si⁴⁺, or adsorbed on the C-S-H charge balancing sulfate ions.     

The effect of two types of C-S-H on the elasticity of cement-based materials: Results from nanoindentation and micromechanical modeling

It has long been recognized, in cement chemistry, that two types of calcium-silicate-hydrate (C-S-H) exist in cement-based materials, but less is known about how the two types of C-S-H affect the mechanical properties. By means of nanoindentation tests on nondegraded and calcium leached cement paste, the paper confirms the existence of two types of C-S-H, and investigates the distinct role played by the two phases on the elastic properties of cement-based materials. It is found that (1) high-density C-S-H are mechanically less affected by calcium leaching than low density C-S-H, and (2) the volume fractions occupied by the two phases in the C-S-H matrix are not affected by calcium leaching. The nanoindentation results also provide quantitative evidence, suggesting that the elastic properties of the C-S-H phase are intrinsic material properties that do not depend on mix proportions of cement-based materials. The material properties and volume fractions are used in a novel two-step homogenization model, that predicts the macroscopic elastic properties of cement pastes with high accuracy. Combined with advanced physical chemistry models that allow, for a given w/c ratio, determination of the volume fractions of the two types of C-S-H, the model can be applied to any cement paste, with or without Portlandite, Clinker, and so on. In particular, from an application of the model to decalcified cement pastes, it is shown that that the decalcification of the C-S-H phase is the primary source of the macroscopic elastic modulus degradation, that dominates over the effect of the dissolution of Portlandite in cement-based material systems.     

钢渣水化产物的特性(英文)

用X射线衍射分析、水化热的测量、化学结合水量的测定、孔结构的测定、扫描电镜观察及强度测试研究了钢渣的水化产物的特性。结果表明:钢渣硬化浆体中主要含有水化硅酸钙(C–S–H)凝胶、Ca(OH)2、惰性组分[RO相、铁酸二钙(C2F)和Fe3O4]和未水化的胶凝相[硅酸三钙(C3S)和硅酸二钙(C2S)];总体而言,钢渣的水化过程与水泥的水化过程相似;钢渣早期的水化速率远低于水泥,但钢渣后期,尤其是90d之后的水化速率高于水泥的。钢渣水化产生的C–S–H凝胶不具有良好的胶凝性能,凝胶之间的相互黏结也不牢固,因此钢渣砂浆的强度很低。     

The effects of nano-C-S-H with different polymer stabilizers on early cement hydration

A promising approach to accelerate cement hydration known as “seeding technology” has been discovered using nano-particles to provide additional nucleation sites for growing of C-S-H. Two different types of polymer, polycarboxylate (PCE) and polysulfonate (PSE) were used as stabilizer to synthesize nano-C-S-H via co-precipitation process. The obtained C-S-H-polymer composites were characterized by means of XRD, FTIR, thermogravimetric analysis (TGA), TEM, dynamic laser scattering (DLS), and BET. DLS measurement shows that the particle size of the obtained C-S-H-polymer suspension ranges from 82.6 to 589.9 nm. The results of DLS and BET show that the particle size of the C-S-H particles synthesized using PCE polymer as stabilizer is smaller than those synthesized with PSE polymer, and hence the specific surface area is much higher. FTIR and TGA results confirm the presence of the polymers in the obtained C-S-H composites particles. XRD results indicate that the presence of the polymers reduces the crystallinity of C-S-H due to the absence of the d002 peak at 2θ of 7°. The calorimetry results show that the main hydration peak of cement is dramatically increased by the addition of the C-S-H-polymer composites. It is interestingly found that the acceleration effect of the C-S-H-polymer composites is linearly proportional to the total surface area of the nanoparticles introduced into the cement pastes. At the same time, it is found that the secondary hydration peak, usually known as the sulfate-depletion peak, is greatly advanced by addition of the C-S-H nano-particles in comparison with the blank cement paste. The acceleration effect of the nano-C-S-H is further verified in a pure C₃S system.     

Effects of decalcification on the microstructure and surface area of cement and tricalcium silicate pastes

Thin coupons of white portland cement (WPC) and tricalcium silicate paste were decalcified by leaching in concentrated ammonium nitrate solutions, resulting in calcium-to-silicon molar ratios (C/S) ranging from 3.0 (control) down to 0.3. The microstructure and surface area were measured using both small-angle neutron scattering (SANS) and nitrogen gas sorption. The intensity in the SANS data regime corresponding to the volume fractal C-S-H gel phase increased significantly on leaching, and the total surface area per unit specimen volume measured by SANS doubled on leaching from C/S=3.0 to near C/S=1.0. The nitrogen BET surface area of the WPC pastes, expressed in the same units, increased on decalcification as well, although not as sharply. The primary cause of these changes is a transformation of the high-density “inner product” C-S-H gel, which normally has a low specific surface area as measured by SANS and nitrogen gas sorption, into a morphology with a high specific surface area. The volume fractal exponent corresponding to the C-S-H gel phase decreased with decalcification from 2.3 to 2.0, indicating that the equiaxed 5 nm C-S-H globule building blocks that form the volume fractal microstructure of normal, unleached cement paste are transformed by decalcification into sheetlike structures of increasing thickness.